EP0566413B1 - Verbesserte spritzfähiger Portlandzement enthaltende feuerschützende Zusammensetzungen - Google Patents

Verbesserte spritzfähiger Portlandzement enthaltende feuerschützende Zusammensetzungen Download PDF

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Publication number
EP0566413B1
EP0566413B1 EP93302940A EP93302940A EP0566413B1 EP 0566413 B1 EP0566413 B1 EP 0566413B1 EP 93302940 A EP93302940 A EP 93302940A EP 93302940 A EP93302940 A EP 93302940A EP 0566413 B1 EP0566413 B1 EP 0566413B1
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EP
European Patent Office
Prior art keywords
slurry
stucco
portland cement
application
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP93302940A
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English (en)
French (fr)
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EP0566413A2 (de
EP0566413A3 (de
Inventor
Richard P. Perito
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WR Grace and Co Conn
WR Grace and Co
Original Assignee
WR Grace and Co Conn
WR Grace and Co
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Publication date
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Publication of EP0566413A2 publication Critical patent/EP0566413A2/de
Publication of EP0566413A3 publication Critical patent/EP0566413A3/xx
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00146—Sprayable or pumpable mixtures
    • C04B2111/00155—Sprayable, i.e. concrete-like, materials able to be shaped by spraying instead of by casting, e.g. gunite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • C04B2111/00525—Coating or impregnation materials for metallic surfaces
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures

Definitions

  • the present invention relates to sprayable fireproofing compositions.
  • U.S. Patent Nos. 3,719,513 and 3,839,059 disclose gypsum-based formulations which contain, in addition to the gypsum binder, a lightweight inorganic aggregate such as vermiculite, a fibrous substance such as cellulose and an air entraining agent.
  • gypsum-based formulations which contain, in addition to the gypsum binder, a lightweight inorganic aggregate such as vermiculite, a fibrous substance such as cellulose and an air entraining agent.
  • Such slurries are generally prepared at ground level and are pumped to the point of application, where they are spray applied to the substrate. OWn the point of application exceeds 20 or 30 stories where high rise construction is involved. Accordingly, pumpability of the slurries is an important criteria in their formulation and preparation.
  • the coating mixes must adhere to the substrate both in the slurried state and in the dry state. Also, the mix must set without undue expansion or shrinkage which could result in the formation of cracks that would seriously deter from the insulative value of the dry coating.
  • U. S. patent No. 4,751,024 the disclosure of which is incorporated herein by reference, teaches sprayable cementitious compositions containing shredded polystyrene as a lightweight aggregate in fireproofing compositions.
  • the cementitious binder is preferably gypsum, but may instead be Portland cement. Indeed, Portland cement is typically used as the binder in applications involving high traffic areas, since the cement tends to be stronger than gypsum.
  • one problem associated with Portland cement-based fireproofing compositions is the relatively poor hangability (the thickness of material that can be applied in a single application) thereof with respect to gypsum-based compositions, since water tends to segregate in Portland cement mixtures in view of the relatively slow hydration process.
  • only one spray application can be made per day on a given substrate. Where the thickness of that spray application is insufficient, a second application cannot be made until the first application sets. Premature attempts to coat a second application result in fall off. If multiple applications cannot be made in a typical eight hour work day, labor costs necessarily increase, as does the time in which a job can be completed.
  • alum does not accelerate Portland cement in sufficient time to allow multiple passes in one day.
  • sodium aluminate should not be used as an accelerator, in view of the corrosive nature of the sodium aluminate, which causes severe corrosion to the hot rolled steel substrates.
  • the fireproofing industry has long sought a Portland cement-based sprayable fireproofing material that can be applied to substrates such as steel in multiple applications per day, and that exhibits improved hangability notwithstanding such multiple applications.
  • the sprayable fireproofing compositions of the instant invention comprise a Portland cement based material that is mixed with water in a conventional paddle mixer and is pumped through various types of equipment. The material is spray applied onto steel beams and columns.
  • the product is produced by dry blending a mixture of Portland cement, stucco (defined herein as calcium sulfate hemi-hydrate), and other additives, such as shredded expanded polystyrene, starch, adhesives and cement strength enhancers.
  • the dry compositions form pumpable, sprayable slurries.
  • an accelerator is added, most preferably in close proximity to the point of injection.
  • the inventor of the present invention has found that causing a set acceleration of the Portland cement-based fireproofing enables multiple pass applications and improved hangability. That set acceleration can be caused by the addition of stucco, which can be sufficiently retarded to allow pumping and spraying, such as with a retarder, preferably a proteinaceous high strength retarder (commecially available from U.S. Gypsum), in an amount of about 0 to about 1.0% by weight of the composition, preferably about 0 to 0.6%.
  • the amount of retarder may vary, depending upon the particular cement and stucco being used.
  • the acceleration of the set is evidenced by initial quicker stiffening of the Portland cemendstucco matrix.
  • the instant fireproofing compositions preferably contain shredded expanded polystyrene as an aggregate.
  • the hangability of the instant composition may depend in part on minimizing the amount of non-shredded expanded polystyrene in the composition.
  • the "shreddedness" of the expanded polystyrene preferably conforms to a particular particle size distribution expressed in terms of the amount of particles retained on a standard #12 sieve (having 0.0661 inch holes), and the amount of particles passing through a standard #30 sieve and retained on a #325 sieve, as determined in accordance with the method described in U.S. Patent No. 4,989,464 (the disclosure of which is hereby incorporated by reference).
  • Suitable amounts of particles retained on the #12 sieve are from about 0 to about 20%, with from about 0 to about 10% being preferred.
  • Suitable amounts of particles passing through a #30 sieve (having 0.0234 inch holes) and retained on a #325 sieve (having 0.0017 inch holes) are less than about 40% by weight, preferably less than about 30%.
  • the preparation and application processes may span many hours and thus the setting time of the mix is generally heavily retarded to provide an acceptable field pot life.
  • This retarding in the mixer contradicts the desired quick setting time upon spray application, and thus a delicate balance of retarding and accelerating is difficult to achieve.
  • the mixture to stiffen substantially in the hopper it would be rendered non-pumpable and therefore would be useless for the intended application.
  • the retarded material does not stiffen as quickly in the mixer, and the retarder does not have any significant effect on the quick stiffening at the nozzle. For these reasons, the addition of retarder is preferred.
  • any set accelerating agent capable of satisfactorily offsetting the retardation of the slurry without deleteriously effecting the slurry or the substrate which is the subject of the application can be used.
  • the accelerator is used in an amount sufficient to sufficiently set the slurry within 1.5 hours of spray application to allow for a second spray application without fall off.
  • the particular amount required will depend upon the type of accelerator, as well as the nature of the various other components of the fireproofing composition.
  • useful accelerators include aluminum sulfate, aluminum nitrate, ferric nitrate, ferric sulfate, potassium sulfate, sulfuric acid, sodium carbonate, sodium bicarbonate and acetic acid, with alum being especially preferred.
  • the present invention is applicable to Portland cement types 1 through 5, although types 1 is especially preferred.
  • the dry mix has a bulk density in the 10 to 18 pcf range, preferably in the 12 to 15 pcf range, and the final dry density of the product is in the 15 to 30 pct range, preferably the 22 to 26 pcf range.
  • the dry material is mixed with water at a ratio of 1.3:1 - 1.6:1 (water:solids).
  • a suitable product can be produced in accordance with the invention by dry blending a mixture of the following: Portland cement 50 - 90% Stucco 4 - 30% Retarder 0 - 1% Shredded polystyrene 0 - 5%, preferably 2 - 3% Clay 2 - 8% Cellulose (aggregate) 0 - 8% Air entrainment 0.2 - 2% Glass fibers 0 - 4% methyl cellulose 0 - 1%
  • a preferred product includes the following range of ingredients: Portland cement 67 - 74% Stucco 12 - 18% Retarder 0 - 0.6% Shredded polystyrene 2.5 - 3%, Clay (thickener) 2 - 6% Cellulose 2 - 6% Air entrainment 0.2 - 0.5% Glass fibers 1.5 - 3% methyl cellulose 0.2 - 0.5% biocide (Amical/wp sold by Angus Chemical) 0.02%, or an amount sufficient to prevent deleterious formation of bacteria
  • the aluminum sulfate set accelerator is used as a 37% solution and is injected into the slurry at the spray nozzle at a level up to 3%.
  • Additional optional ingredients may be added, such as glass fibers to control shrinkage, methyl cellulose or other suitable thickeners known to those skilled in the art, air entraining agents such as sodium lauryl sulfate, and a biocide to inhibit bacterial formation.
  • a second application can be spray applied within about 1 to 2 hours, preferably within about 1.5 hours of the first application without fall off. Improved hangability also resulted; a single application typically could be spray applied to a thickness of about 19 to 25 mm (3/4 - 1 inch), and was in fact spray applied to a thickness of as much a 38 mm (1.5 inches), whereas conventional Portland cement-based compositions typically could be hung to thicknesses of only 13 to 16 mm (1/2 to 5/8 inches).
  • the 12% and 16% first application had a thickness of 19 to 22 mm (3/4" to 7/8"), with a total average thickness after the second application up to 38 - 51 mm (1.5-2").
  • the first application amounted to a coating of up to 16 mm (5/8 of an inch).
  • a second pass (amounting to a total coating thickness of 38 mm (1.5 inches)) was attempted after 1.5 hours, but fall off was encountered.
  • the application of a second pass caused fall off of not only the second application, but also some of the coating from a first application. This suggests that the coating of the first applicaiton did not sufficiently bond to the substrate within the 1.5 hour time period.
  • the vicat data is a measurement of the low and stiffness of the material.
  • the stiffness is generally an indication of how well the product hangs. The lower the vicat reading, the stiffer the product. Preferably the vicat number is below about 10 mm, most preferably the reading is about 8 mm or less.
  • the vicat reading of formulation number 4 in Example 1 seems excellent, in fact that formulation, containg 24% stucco, proved to be too stiff in the hopper; that is, the workability was poor. In order to render such a formulation commerically viable, additional water would have been necessary, thereby increasing the final vicat number of the useable composition.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Building Environments (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
  • Fireproofing Substances (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Claims (15)

  1. Spritzbare, feuerfest machende Zusammensetzung auf Portlandzementbasis, die Portlandzement, Stuck und einen Abbindebeschleuniger umfaßt.
  2. Zusammensetzung nach Anspruch 1, die außerdem einen Stuck-Abbindeverzögerer umfaßt.
  3. Zusammensetzung nach Anspruch 1 oder 2, die außerdem zerkleinertes Polystyrol umfaßt.
  4. Trockenzusammensetzung, die Portlandzement und Stuck umfaßt und bei Zugabe von Wasser eine abbindende Aufschlämmung ergibt, die durch Spritzen auf ein Stahlsubstrat aufbringbar ist, um im aufgeschlämmten Zustand und nach dem Abbinden an dem Substrat zu haften, wobei die Aufschlammung beim Spritzen einen Abbindebeschleuniger in einer solchen Menge einschließt, daß die Aufschlämmung nach der Spritzaufbringung innerhalb von acht Stunden ausreichend abbindet, um mindestens eine zweite Spritzaufbringung der Aufschlammung hierauf zuzulassen.
  5. Trockenzusammensetzung nach Anspruch 4, die außerdem einen Stuck-Abbindeverzögerer umfaßt.
  6. Trockenzusammensetzung nach Anspruch 4 oder 5, bei der der Abbindebeschleuniger und der Stuck in Mengen vorhanden sind, so daß die Aufschlämmung nach der Spritzaufbringung innerhalb von ein bis zwei Stunden ausreichend abbindet, um mindestens eine zweite Spritzaufbringung der Aufschlämmung hierauf zuzulassen.
  7. Trockenzusammensetzung nach Anspruch 4, 5 oder 6, die außerdem zerkleinertes Polystyrol umfaßt.
  8. Verfahren zum Aufbringen einer Beschichtung aus einer spritzbaren, feuerfest machenden Zusammensetzung auf ein Stahlsubstrat, bei dem Wasser zu einer Trockenzusammensetzung gegeben wird, die Portlandzement und Stuck umfaßt, um eine spritzbare Aufschlämmung zu bilden, die Aufschlämmung zu einer Spritzdüse gefördert wird, vor, während oder nach dem Fördervorgang nahe an der Düse ein Abbindebeschleuniger in die Aufschlämmung eingebracht wird und eine Beschichtung aus der Aufschlämmung auf das Substrat gespritzt wird.
  9. Verfahren nach Anspruch 8, bei dem die Schicht aus der Aufschlämmung mit einer Dicke aufgebracht wird, die 16 mm (5/8 inch) übersteigt.
  10. Verfahren nach Anspruch 8 oder 9, bei dem mehrere Beschichtungen aus spritzbarer, feuerfest machender Zusammensetzung aufgebracht werden, wobei außerdem die erste Schicht in ausreichendem Maße abbinden gelassen wird, um eine zweite Schicht zu tragen, und eine zweite Schicht der Aufschlämmung auf diese aufgebracht wird.
  11. Verfahren nach Anspruch 10, bei dem die durchschnittliche Gesamtdicke der ersten und zweiten Schicht aus der Aufschlämmung 12 bis 25 mm (1,5 bis 2 inch) beträgt.
  12. Verfahren nach einem der Ansprüche 8 bis 11, bei dem die Trockenzusammensetzung außerdem einen Stuck-Abbindeverzögerer umfaßt.
  13. Verfahren nach Anspruch 12, bei dem der Stuck, der Stuck-Abbindeverzögerer und die Abbindebeschleuniger in ausreichenden Mengen bereitgestellt werden, um die Aufschlämmung daran zu hindern, in einem Ausmaß abzubinden, das den Fördervorgang verhindert, während es der Aufschlämmung bei Aufbringung auf das Substrat möglich ist, innerhalb eines Zeitraums von höchstens acht Stunden in einem ausreichenden Ausmaß abzubinden, so daß eine zweite Aufbringung der Aufschlämmung auf das Substrat möglich ist, ohne ein Ablösen zu verursachen.
  14. Verfahren nach Anspruch 13, bei dem der Stuck, der Stuck-Abbindeverzögerer und die Abbindebeschleuniger in ausreichenden Mengen bereitgestellt werden, so daß es der Aufschlämmung bei Aufbringung auf das Substrat möglich ist, innerhalb von 1,5 Stunden abzubinden.
  15. Verfahren nach einem der Ansprüche 8 bis 14, bei dem die Trockenzusammensetzung außerdem zerkleinertes Polystyrol umfaßt.
EP93302940A 1992-04-16 1993-04-15 Verbesserte spritzfähiger Portlandzement enthaltende feuerschützende Zusammensetzungen Expired - Lifetime EP0566413B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US869605 1992-04-16
US07/869,605 US5340612A (en) 1992-04-16 1992-04-16 Sprayable portland cement-based fireproofing compositions

Publications (3)

Publication Number Publication Date
EP0566413A2 EP0566413A2 (de) 1993-10-20
EP0566413A3 EP0566413A3 (de) 1994-01-19
EP0566413B1 true EP0566413B1 (de) 1997-01-29

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EP93302940A Expired - Lifetime EP0566413B1 (de) 1992-04-16 1993-04-15 Verbesserte spritzfähiger Portlandzement enthaltende feuerschützende Zusammensetzungen

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Country Link
US (1) US5340612A (de)
EP (1) EP0566413B1 (de)
JP (1) JP3595561B2 (de)
KR (1) KR100240296B1 (de)
CN (1) CN1066421C (de)
AT (1) ATE148435T1 (de)
AU (1) AU663579B2 (de)
CA (1) CA2094112C (de)
DE (1) DE69307763T2 (de)
ES (1) ES2097447T3 (de)
HK (1) HK1000350A1 (de)
MY (1) MY108740A (de)
TW (1) TW235289B (de)
ZA (1) ZA932655B (de)

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US4934596A (en) * 1989-01-19 1990-06-19 W. R. Grace & Co.-Conn. Slurry distributor
US4989464A (en) * 1989-07-25 1991-02-05 W. R. Grace & Co.-Conn. Method and apparatus for determining particle size distribution
US4953620A (en) * 1989-08-14 1990-09-04 Atlantic Richfield Company Accelerating set of retarded cement
DE3937432C2 (de) * 1989-11-10 1997-02-13 Knauf Westdeutsche Gips Bindemittel und seine Verwendung
CH680730A5 (de) * 1990-07-09 1992-10-30 Sika Ag

Also Published As

Publication number Publication date
JPH06271853A (ja) 1994-09-27
CA2094112A1 (en) 1993-10-17
AU663579B2 (en) 1995-10-12
DE69307763D1 (de) 1997-03-13
CN1066421C (zh) 2001-05-30
EP0566413A2 (de) 1993-10-20
EP0566413A3 (de) 1994-01-19
AU3689993A (en) 1993-10-21
KR100240296B1 (ko) 2000-01-15
MY108740A (en) 1996-11-30
JP3595561B2 (ja) 2004-12-02
ATE148435T1 (de) 1997-02-15
ZA932655B (en) 1993-10-25
HK1000350A1 (en) 1998-03-06
US5340612A (en) 1994-08-23
CA2094112C (en) 2004-11-23
TW235289B (de) 1994-12-01
CN1083453A (zh) 1994-03-09
DE69307763T2 (de) 1997-05-28
ES2097447T3 (es) 1997-04-01
KR930021570A (ko) 1993-11-22

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